Norbornyl esters and uses thereof in augmenting or enhancing the organoleptic properties of a consumable material and process for preparing same

ABSTRACT

Described is a genus of compounds defined according to the structure: ##STR1## hereinafter termed &#34;norbornyl esters&#34; wherein R 1 , R 2  and R 3  represent methyl or hydrogen with the proviso that at least one of R 1 , R 2  and R 3  is hydrogen as well as uses thereof in augmenting or enhancing the aroma or taste of consumable materials including foodstuffs, chewing gums, medicinal products, toothpastes, chewing tobaccos, smoking tobaccos, smoking tobacco articles, perfume compositions, colognes and perfumed articles (including, but not limited to, solid or liquid anionic, cationic, nonionic or zwitterionic detergents, fabric softener compositions, fabric softener articles, hair preparations and perfumed polymers). Also described is a novel process for preparing such norbornyl esters.

BACKGROUND OF THE INVENTION

The present invention relates to substituted norbornyl ester derivativesof the genus of compounds having the structure: ##STR2## wherein R₁, R₂and R₃ represents methyl or hydrogen with at least one of R₁, R₂ and R₃being hydrogen and uses thereof in order to alter, modify or enhance thearoma or taste of consumable materials.

There has been considerable work performed relating to substances whichcan be used to impart (modify, augment or enhance) fragrances and tastesto (or in) various consumable materials. The substances are used todiminish the use of natural materials some of which may be in shortsupply and to provide more uniform properties in the finished product.

Sweet, amber-like, powderful long-lasting green, herbaceous, floral,fruity, powerful anisic and bergamot-like aroma nuances are desirable inseveral types of perfume compositions, perfumed articles and colognes.

Sweet, licorice-like, anise oil-like, spicy, fresh dandelion leaf andraw spinach aroma and taste nuances with faint scallion-like nuances aredesirable in augmenting or enhancing the aroma and/or taste offoodstuffs, chewing gums, medicinal products, chewing tobaccos andtoothpastes.

Turkish-like tobacco nuances are particularly desirable in augmenting orenhancing the aroma or taste of smoking tobacco and smoking tobaccoarticle components both prior to smoking and on smoking in the mainstream and the side stream.

The perfume use of norbornene alcohol and ester derivatives having thestructures: ##STR3## wherein R₁ is C₁ -C₄ alkyl is disclosed in U.S.Pat. No. 3,860,635 particularly at Example XV at column 16 thereof. Suchcompounds and the syntheses thereof are also disclosed by Bobyleva, Zh.Org. Kh. Volume 13, No. 10, pages 2085-92, October 1977. In addition,ethers of norbornene derivatives having the structures: ##STR4## aredisclosed as well as the process for preparing same according to thereaction: ##STR5## in Shield, Can. J. Chem. Volume 49, 1971, page 1142.

U.S. Pat. No. 3,927,116 indicates the utility of certain vinyl norbornylethers having the structure: ##STR6## wherein R₂ represents C₁ -C₄ alkylas being intermediate for the preparation of detergents at column 9lines 10-15. No indication in U.S. Pat. No. 3,927,116 of the use of suchcompounds in perfumery, for augmenting or enhancing the aroma ofperfumes, perfumed articles and colognes, is suggested either implicitlyor explicitly in U.S. Pat. No. 3,927,116.

However, the compounds of our invention defined according to thestructure: ##STR7## wherein R₁, R₂ and R₃ represent methyl or hydrogenand at least one of R₁, R₂ and R₃ is hydrogen have unexpected, unobviousand advantageous organoleptic properties in consumable materials overany closely similar compounds of the prior art.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the crude reaction product of Example Icontaining the compound having the structure: ##STR8## (conditions:10'×1/8" SE-30 column programmed at 150°-220° C. at 6° C. per minute).

FIG. 2 is the NMR spectrum from Fraction 5 of the distillation productof the reaction product of Example I containing the compound having thestructure: ##STR9## (Solvent: CFCl₃ ; Field strength: 100 MHz).

FIG. 3 is the infra-red spectrum for Fraction 5 of the distillationproduct of the reaction product of Example I containing the compoundhaving the structure: ##STR10##

FIG. 4 is the GLC profile for the crude reaction product of Example IIcontaining the compound having the structure: ##STR11##

FIG. 5 is the NMR spectrum for Fraction 3 of the distillation product ofthe reaction product of Example II containing the compound having thestructure: ##STR12## (Solvent: CFCl₃ ; Field strength: 100 MHz).

FIG. 6 is the infra-red spectrum for Fraction 3 of the distillationproduct of the reaction product of Example II containing the compoundhaving the structure: ##STR13##

FIG. 7 is the GLC profile for the crude reaction product of Example IIIcontaining the compound having the structure: ##STR14## (cis and transisomer mixture).

FIG. 8 is the NMR spectrum for Fraction 10 of the distillation productof the reaction product of Example III containing the compound havingthe structure: ##STR15## (Solvent: CFCl₃ ; Field strength: 100 MHz).

FIG. 9 is the infra-red spectrum for Fraction 10 of the distillationproduct of the reaction product of Example III containing the compoundhaving the structure: ##STR16##

FIG. 10 is the GLC profile of the crude reaction product of Example IVcontaining the compound having the structure: ##STR17##

FIG. 11 is the NMR spectrum for Fraction 9 of the distillation productof the reaction product of Example IV containing the compound having thestructure: ##STR18## (Solvent: CFCl₃ ; Field strength: 100 MHz).

FIG. 12 is the infra-red spectrum for Fraction 9 of the distillationproduct of the reaction product of Example IV containing the compoundhaving the structure: ##STR19##

DETAILED DESCRIPTION OF THE DRAWINGS

In FIG. 1 which is the GLC profile for the reaction product of Example Icontaining the compound having the structure: ##STR20## the peaksindicated by reference numerals "110" and "111" are the peaks for thereaction product including the major reaction product (greater than 80%)which is the compound having the structure: ##STR21## but also includingother compounds, for example, the compound having the structure:##STR22##

FIG. 4 is the GLC profile of the crude reaction product of Example IIwhich is indicated by peaks "120", "121" and "122". The major peak "121"is the peak for the compound defined according to the structure:##STR23## The additional peaks "120" and "122" are for isomericcompounds including that having the structure: ##STR24##

FIG. 7 is the GLC profile for the reaction product of Example IIIcontaining a major proportion of the compounds having the structures:##STR25##

The major peak "131" is for the compounds having the structures:##STR26## Peaks "130" and "132" are for compounds which are in a minorproportion (20% or less) for example, the compounds having thestructures: ##STR27## All of the compounds defined according to peaks"130", "131" and "132" may be shown according to the genus having thestructure: ##STR28## wherein one of the dashed lines represents acarbon-carbon bond and the other of the dashed lines represents no bondand wherein the wavy lines represent hydrogen and methyl groupsjuxtaposed around the carbon-carbon double bond in a "cis" or "trans"configuration.

FIG. 10 is the GLC profile for the reaction product of Example IVcontaining a major proportion (greater than 80%) of the compound definedaccording to the structure: ##STR29## The peak indicated by referencenumeral "141" is the peak for this compound having the structure:##STR30## The peaks indicated by reference numerals "140" and "142" arefor compounds which are in a minor proportion (less than 20%) such asthat having the structure: ##STR31##

THE INVENTION

It has now been determined that certain substituted norbornyl esterderivatives are capable of imparting a variety of flavors and fragrancesto various consumable materials. Briefly, my invention contemplatesaugmenting or enhancing the flavors and/or fragrances of such consumablematerials by adding thereto a small but effective amount of at least onesuch norbornyl ester derivative defined according to the genericstructure: ##STR32## wherein R₁, R₂ and R₃ represent methyl or hydrogenwith the proviso that at least one of R₁, R₂ and R₃ is hydrogen; andflavoring (e.g. for foodstuffs, chewing gum, chewing tobaccos, medicinalproducts and smoking tobaccos) and fragrance compositions (e.g. perfumecompositions and compositions for augmenting or enhancing the aromas ofperfumed articles such as solid or liquid anionic, cationic, nonionic orzwitterionic detergents or fabric softeners or fabric softener articlesor cosmetic powders or hair preparations or perfumed polymers)containing such norbornyl ester derivatives. The invention alsocontemplates a novel process for producing such substituted norbornylesters.

The norbornyl ester derivatives produced according to the process of myinvention which are used in practicing that part of my inventionconcerning flavoring and fragrance compositions are actually racemicmixtures rather than individual stereoisomers and mixtures of cis andtrans isomers rather than individual cis or trans isomers (as the casemay be).

The norbornyl ester derivatives of my invention insofar as theirfragrance profiles are concerned have sweet, amber-like, powerfullong-lasting green, herbaceous, floral (violet-like), fruity, powerfulanisic and bergamot-like aromas.

Insofar as their flavor uses are concerned, (e.g., foodstuffs, chewinggums, medicinal products, toothpastes and chewing tobaccos), thenorbornyl ester derivatives of my invention have sweet, licorice-like,anise oil-like, spicy, dill-like, fresh dandelion leaf, raw spinach andscallion-like aroma and taste nuances.

Insofar as smoking tobacco falvors and aromas are concerned, thenorbornyl ester derivatives of my invention have Turkish tobacco-likearoma and taste nuances on smoking in both the main stream and the sidestream and also prior to smoking.

The following table sets forth the structure and organoleptic propertyprofiles for specific compounds produced according to the exampleslisted herein and located infra:

                                      TABLE I                                     __________________________________________________________________________                         Fragrance                                                                              Food Flavor                                     Structure            Profile  Profile                                         __________________________________________________________________________     ##STR33##           Sweet, anisic, amber-like aroma with                                          green, herbaceous top notes.                                                           A sweet, licorice-like, anise oil-like,                                       spicy (dill- like) aroma and taste profile                                    at 0.1 ppm causing it to be useful for                                        licorice, spearmint and mouthwash flavors.      (produced according to                                                        Example I)                                                                     ##STR34##           A powerful long-lasting green, herbaceous aroma.                                       A fresh dandelion leaf, raw spinich aroma                                     and taste with faint scallion-like nuances                                    at 0.01 ppm causing it to be extremely                                        useful in salad dressing flavors.               (produced according to                                                        Example II)                                                                    ##STR35##           A floral (violet- like), green, fruity aroma                                  profile. A fresh dandelion-like, raw spinach- like                                     aroma and taste profile at 0.3 ppm causing                                    it to be extremely useful in salad dressing                                   flavors.                                        and                                                                            ##STR36##                                                                    (produced according to                                                        Example III)                                                                   ##STR37##           A powerful anisic, bergamot-like, fruity aroma with                           a citronellal- like undertone.                                                         A sweet, licorice-like aroma and taste                                        profile at 0.001 ppm.                           (produced according to                                                        Example IV)                                                                   __________________________________________________________________________

The compounds of my invention may be prepared by reacting ethylidenenorbornene having the structure: ##STR38## with an acrylic acidderivative defined according to the structure: ##STR39## wherein R₁, R₂and R₃ may be hydrogen or methyl with the proviso that at least one ofR₁, R₂ and R₃ is hydrogen in the presence of a catalyst which is eithera mineral acid or a Lewis acid. Examples of mineral acid catalysts aresulfuric acid, phosphoric acid, para-toluene sulfonic acid, methanesulfonic acid and acid ion exchange resins. Examples of Lewis acidswhich can be used as catalysts are boron trifluoride etherate, borontrifluoride, aluminum chloride, zinc chloride, stannic chloride,stannous chloride, zinc bromide, diethyl aluminum chloride, ethylaluminum dichloride, ethyl aluminum dibromide and diethyl aluminumdibromide. The reaction preferably takes place in the presence of aninert solvent such as tetrahydrofuran, toluene or benzene. The reactionmay take place in the absence of the inert solvent and in the presenceof an excess of the acrylic acid derivative reactant, the excess of theacrylic acid derivative reactant being used as the "solvent".

The reaction temperature may vary from about 25° C. up to about 120° C.with reflux temperatures being preferred. The reflux temperature dependson the pressure in the reactor and the particular solvent being used aswell as its concentration in the reaction mass. The mole ratio of acidcatalyst to ethylidene norbornene may vary from about 1:99 up to about1:10. The mole ratio of ethylidene norbornene reactant to acrylic acidderivative reactant may vary from about 1:1 up to about 1:2 with a moleratio of about 1:1 of norbornene:acrylic acid derivative reactant beingpreferred. Thus, the reaction to produce the compounds of my inventionmay be shown thusly: ##STR40## with the compound produced being thecompound in greatest proportion (80% or more) in the reaction productmixture. The reaction in more general terms, however, may be shownthusly: ##STR41## wherein the wavy lines in the acrylic acid reactantstructure and in the norbornyl ester derivative are indicative of a"cis" or "trans" juxtaposition of the R₁, R₂, R₃ and carboxylic acidmoieties around the carbon-carbon double bond or the R₁, R₂, R₃ andcarboalkoxy moieties around the carbon-carbon double bond. The term"[K]" represents the catalyst; that is, the Lewis acid catalyst or theprotonic acid catalyst as set forth above. The dashed lines in thereaction product represent carbon-carbon bonds or no bonds. Thus, thereaction product which is shown according to the structure: ##STR42## inthis more generalized equation represents compounds having thestructure: ##STR43## (which is present in greater than 80%concentration) as well as the compounds having the structure: ##STR44##(which are present in less than 20% proportions in the reaction mass)(on a solvent-free basis).

Structures of these isomers are as follows: ##STR45## wherein Rrepresents acrylyl, methacrylyl, crotonyl or senecioilyl.

The norbornyl ester derivative(s) and one or more auxiliary perfumeingredients, including, for example, hydrocarbons, alcohols, ketones,aldehydes, nitriles, esters other than said norbornyl ester derivatives,lactones, ethers, hydrocarbons, synthetic essential oils, and naturalessential oils may be admixed so that the combined odors of theindividual components produce a pleasant and desired fragrance,particularly and preferably in the amber, citrusy, anisic and floralfragrances. Such perfume compositions usually contain (a) the main noteor the "bouquet" or foundation stone of the composition; (b) modifierswhich round off and accompany the main note; (c) fixatives which includeodorous substances which lend a particular note to the perfumethroughout all stages of evaporation and substances which retardevaporation and (d) topnotes which are usually low-boiling,fresh-smelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however, theoverall sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, one or moreof the norbornyl ester derivatives of my invention can be used to alter,modify or enhance the aroma characteristic of a perfume composition, forexample, by utilizing or moderating the olfactory reaction contributedby another ingredient in the composition.

The amount of norbornyl ester derivative of my invention which will beeffective in perfume compositions as well as in perfumed articles andcolognes depends upon many factors including the other ingredients,their amounts and the effects which are desired. It has been found thatperfume compositions containing as little as 0.005% of norbornyl esterderivative(s) or even less (e.g. 0.002%) can be used to impart sweet,amber-like, powerful long-lasting green, herbaceous, floral,violet-like, fruity, powerful anisic and bergamot-like aromas withcitronellal-like undertones to soaps, cosmetics, detergents (includinganionic, cationic, nonionic or zwitterionic solid or liquid detergents)perfumed polymers or other products. The amount employed can range up to70% of the fragrance components and will depend upon the considerationsof cost, nature of the end product, the effect desired on the finishedproduct and the particular fragrance sought.

The norbornyl ester derivative(s) of my invention are useful (takenalone or taken together with other ingredients in perfume compositions)in detergents, soaps, space odorants and deodorants, perfumes, colognes,toilet waters, bath preparations, hair preparations such as lacquers,brilliantines, pomades and shampoos; cosmetic preparations such ascreams, deodorants, hand lotions and sun screens; powders such as talcs,dusting powders, face powders and the like.

As little as 0.25% of the norbornyl ester derivatives will suffice toimpart an intense, sweet, amber-like, powerful long-lasting green,herbaceous, floral, fruity, powerful anisic, bergamot-like aroma tocitrusy, floral, amber and anisic perfume formulations. Generally nomore than 5% of the norbornyl ester derivative(s) based on the ultimateend product is required to be used in the perfume composition.

Furthermore, as little as 0.25% of the norbornyl ester derivatives willsuffice to impart such aroma to perfumed articles per se, whether in thepresence of other perfume materials or whether used by themselves. Thus,the range of use of the norbornyl ester derivative(s) of my invention inperfumed articles, e.g. perfumed polymers and solid or liquid anionic,cationic, nonionic or zwitterionic detergents, may vary from 0.25% up toabout 5% by weight based on the total weight of the perfumed article.

In addition, the perfume composition or fragrance composition of myinvention can contain a vehicle or carrier for the norbornyl esterderivative(s). The vehicle can be a liquid such as a non-toxic alcohol,e.g. ethanol, a non-toxic glycol, e.g. propylene glycol, or the like.The carrier can also be an absorbent solid such as a gum (e.g. gumarabic or xanthan gum or guar gum) or components for encapsulating thecomposition by means of coacervation (such as by gelatin) or by means offormation of a polymer around a liquid center (as by using a ureaformaldehyde prepolymer to form a polymeric capsule around a perfumecomposition center).

It will be appreciated from the present disclosure that the norbornylester derivatives according to the present invention can be used toalter, vary, fortify, modify, enhance or otherwise improve the flavor ofa wide variety of materials which are ingested, consumed or otherwiseorganoleptically sensed.

The terms "alter" and "modify" in their various forms will be understoodherein to mean the supplying or imparting of a flavor character or noteto an otherwise bland, relatively tasteless substance, or augmenting anexisting flavor characteristic where the natural flavor is deficient insome regard or supplementing the existing flavor impression to modifytheir organoleptic character.

The term "enhance" is intended herein to mean the intensification (byuse of the norbornyl ester derivative of my invention) of a flavor oraroma note or nuance in a tobacco flavor or foodstuff or perfumecomposition or perfumed article without changing the quality of saidnote or nuance.

A "flavoring composition" is taken to mean one which contributes a partof the overall flavor impression by supplementing or fortifying anatural or artificial flavor in a material or one which suppliessubstantially all the flavor and/or aroma character to a consumablearticle.

The term "foodstuff" as used herein includes both solid and liquidingestible materials for man or animals which materials usually do, butneed not, have nutritional value. Thus, foodstuffs include meats,gravies, soups, convenience foods, malt, alcoholic and other beverages,milk and dairy products, seafoods, including fish, crustaceans, mollusksand the like, candies, vegetables, cereals, soft drinks, snacks, dog andcat food, other veterinary products, and the like. The norbornyl esterderivatives of my invention are also useful tobacco flavorants andflavor enhancers.

The term "tobacco" will be understood herein to mean natural productssuch as, for example, burley, Turkish tobacco, Maryland tobacco,flue-cured tobacco and the like including tobacco-like or tobacco-basedproducts such as reconstituted by homogenized leaf and the like as wellas tobacco substitutes intended to replace natural tobacco such aslettuce and cabbage leaves and the like. The tobaccos and tobaccoproducts in which the norbornylester derivatives of my invention areuseful include those designed or used for smoking such as in cigarettes,cigar and pipe tobacco, as well as products such as snuff, chewingtobacco and the like.

When the norbornyl ester derivatives of this invention are used in aflavoring composition, they can be combined with conventional flavoringmaterials or adjuvants. Such co-ingredients or flavoring adjuvants arewell known in the art for such use and have been extensively describedin the literature. Requirements of such adjuvant materials are: (1) thatthey be non-reactive with the norbornyl ester derivatives of myinvention; (2) that they be organoleptically compatible with thenorbornyl ester derivatives of my invention whereby the flavor of theultimate consumable material to which the norbornyl ester derivativesare added is not detrimentally affected by the use of the adjuvant; (3)that they be ingestibly acceptable and thus non-toxic or otherwisenon-deleterious. Apart from these requirements, conventional materialscan be used and broadly include other flavor materials, vehicles,stabilizers, thickeners, surface active agents, conditioners, and flavorintensifiers.

Such conventional flavoring materials include saturated fatty acids,unsaturated fatty acids and amino acids; alcohols including primary andsecondary alcohols, esters, carbonyl compounds including ketons andaldehydes; lactones; other cyclic organic materials including benzenederivatives, allicyclic compounds, heterocyclics such as furans,pyridines, pyrazines and the like; sulfur-containing compounds includingthiols, sulfides, disulfides and the like; proteins; lipids,carbohydrates; so-called flavor potentiators such as monosodiumglutamate, magnesium glutamate, calcium glutamate, guanylates andinosinates; natural flavoring materials such as cocoa, vanilla andcaramel; essential oils and extracts such as anise oil, clove oil andthe like and artificial flavoring materials such as vanillin and thelike.

Specific preferred flavor adjuvants are as follows:

anise oil;

ethyl-2-methyl butyrate;

vanillin;

cis-3-heptenol;

cis-3-hexenol;

trans-2-heptenol;

cis-3-heptenal;

butyl valerate;

2,3-diethyl pyrazine;

methyl cyclopentenolone;

benzaldehyde;

valerian oil;

3,4-dimethoxyphenol;

amyl acetate;

amyl cinnamate;

gamma butyryl lactone;

furfural;

benzaldehyde;

trimethyl pyrazine;

phenyl acetic acid;

isovaleraldehyde;

ethyl maltol;

ethyl vanillin;

ethyl valerate;

ethyl butyrate;

cocoa extract;

coffee extract;

peppermint oil;

spearmint oil;

clove oil;

anethol;

cardamom oil;

wintergreen oil;

cinnamic aldehyde;

2,3-diethyl pyrazine;

ethyl-2-methyl valerate;

gamma hexenyl lactone;

2,4-decadienal;

2,4-heptadienal;

butylidene phthalide.

According to another aspect of my invention, an organolepticallyimproved smoking tobacco product and additives therefor as well asmethods of making the same which overcome specific problems heretoforeencountered in which specific Turkish, oriental-like aromas prior tosmoking and improved Turkish, oriental aromas on smoking in the mainstream and the side stream are created or enhanced or modified oraugmented and may be readily controlled and maintained at the desireduniform level regardless of variations in the tobacco components of theblend. In particular, low grade Virginia-type tobaccos may be upgradedusing the norbornyl ester derivatives of my invention.

This invention further provides improved tobacco additives and methodswhereby various desirable natural aromatic Turkish tobacco flavoringcharacteristics with oriental notes may be imparted to smoking tobaccoproducts and may be readily varied and controlled to produce the desireduniform flavoring characteristics.

In carrying out this aspect of my invention, I add to smoking tobaccomaterials or a suitable substitute therefor (e.g. dried lettuce leaves)an aroma and flavor additive containing as an active ingredient one ormore of the norbornyl esters of my invention.

In addition to the norbornyl esters of my invention, other flavoring andaroma additives may be added to the smoking tobacco material orsubstitute therefor either separately or in admixture with the norbornylester derivatives of my invention as follows:

I. Synthetic materials:

Beta-ethyl-cinnamaldehyde;

Eugenol;

Dipentene;

Beta-damascenone;

Maltol;

Ethyl maltol;

Delta undecalactone;

Delta decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-hexenol-1;

2-methyl-5-isopropyl-1,3-nonadiene-8-one;

2,6-dimethyl-2,6-undecadiene-10-one;

2-methyl-5-isopropyl acetophenone;

2-hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethyl naphtho(2,1-b)-furan;

4-hydroxy hexanoic acid, gamma lactone; and

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372 issued on June 29, 1971.

II. Natural oils:

Celery seed oil;

Coffee extract;

Bergamot oil;

Cocoa extract;

Nutmeg oil; and

Origanum oil.

An aroma and flavoring concentrate containing one or more of thenorbornyl ester derivatives of my invention and, if desired, one or moreof the above indicated additional flavoring additives may be added tothe smoking tobacco material, to the filter or to the leaf or paperwrapper. The smoking tobacco material may be shredded, cured, cased andblended tobacco material or reconstituted tobacco material or tobaccosubstitutes (e.g. lettuce leaves) or mixtures thereof. The proportionsof flavoring additives may be varied in accordance with taste butinsofar as enhancement or the imparting of oriental and/or Turkishtobacco notes, I have found that satisfactory results are obtained ifthe proportion by weight of the sum total of norbornyl esters to smokingtobacco material is between 50 ppm and 1,500 ppm (0.005%-0.15%) of theactive ingredients to the smoking tobacco material. I have further foundthat satisfactory results are obtained if the proportion by weight ofthe sum total of norbornyl ester derivatives used to flavoring materialis between 500 and 15,000 ppm (0.05%-1.5%).

Any convenient method for incorporating the norbornyl esters into thetobacco product may be employed. Thus, the norbornyl ester derivativestaken alone or along with other flavoring additives may be dissolved ina suitable solvent such as ethanol diethylether and/or volatile organicsolvents and the resulting solution may either be spread onto the cured,cased, and blended tobacco material or the tobacco material may bedipped into such solution. Under certain circumstances, a solution ofthe norbornyl esters taken alone or taken further together with otherflavoring additives as set forth above may be applied by means of asuitable applicator such as a brush or roller on the paper or leafwrapper for the smoking product, or it may be applied to the filter byeither spraying or dipping or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated and the thus-treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated may have the norbornyl esterderivatives in excess of the amounts or concentrations above indicatedso that when blended with other tobaccos, the final product will havethe percentage within the indicated range.

In accordance with one specific example of my invention, an aged, curedand shredded domestic Virginia tobacco is spread with a 20% alcoholsolution of the compound having the structure: ##STR46## producedaccording to Example I, infra, in an amount to provide a tobaccocomposition containing 100 ppm by weight of the compound having thestructure: ##STR47## on a dry basis. Thereafter the alcohol is removedby evaporation and the tobacco is manufactured into cigarettes by theusual techniques. The cigarette, when treated as indicated, has adesired and pleasing aroma which is detectable in the main stream andthe side stream when the cigarette is smoked. This aroma is described asbeing sweeter, with pronounced Turkish/oriental characteristics and withimproved body and enhanced tobacco character in the main stream and sidestream. In addition, interesting amber nuances are imparted.

While my invention is particularly useful in the manufacture of smokingtobacco such as cigarette tobacco, cigar tobacco and pipe tobacco, othertobacco products formed from sheeted tobacco dust or fines may also beused. Likewise the norbornyl esters of my invention can be incorporatedwith materials such as filter tip materials, seam paste, packagingmaterials and the like which are used along with tobacco to form aproduct adapted for smoking. Furthermore, the norbornyl esters can beadded to certain tobacco substitutes of natural or synthetic origin(e.g. dried lettuce leaves) and, accordingly, by the term "tobacco" asused throughout this specification, is meant any composition intendedfor human consumption by smoking or otherwise when composed of tobaccoplant parts or substitute materials or both.

The following examples are given to illustrate embodiments of theinvention as it is presently preferred to practice it. It will beunderstood that these examples are illustrative and the invention is notto be considered restricted thereto except as indicated in the appendedclaims.

EXAMPLE I Preparation of acrylic acid ester of5-ethyl-tricyclo[2.2.1.0(2,6)]heptan-1-ol ##STR48##

Into a 2 liter reaction flask equipped with stirrer, thermometer,heating mantle and reflux condenser is placed 30 ml borontrifluoride anddiethyletherate and 300 ml anhydrous toluene. While maintaining thereaction mass at 25°-34° C., a mixture of 288 grams (4 moles) of acrylicacid and 480 grams (4 moles) of ethylidene norbornene are added to thereaction mass over a 35 minute period. The temperature over the 35minute period is maintained at 25°-34° C. The reaction mass is thenstirred at 25°-34° C. for a period of 20 minutes.

The reaction mass is then washed as follows:

i. 500 ml 10% aqueous sodium chloride

ii. two volumes of 10% sodium chloride

iii. 10% aqueous sodium chloride

iv. 500 ml 5% sodium hydroxide

v. 500 ml 10% aqueous sodium chloride

vi. 500 ml 10% aqueous sodium chloride.

The reaction mass is then dried over anhydrous magnesium sulfate anddistilled on a 12"×1.5" Goodloe column yielding the following fractions:

    ______________________________________                                               Vapor      Liquid                                                      Fraction                                                                             Temp.      Temp.   Pressure  Reflux                                    Number (°C.)                                                                             (°C.)                                                                          mm/Hg.    Ratio                                     ______________________________________                                        1      41/44      72/117  50        2:1                                       2      96         110     3         2:1                                       3      82          97     3         2:1                                       4      82         100     3         1:1                                       5      83         100     3         100% takeoff                              6      83         104     3         100% takeoff                              7      82         130     3         100% takeoff                              ______________________________________                                    

FIG. 1 is the GLC profile for the crude reaction product prior todistillation (conditions: 10'×0.125" SE-30 column programmed at150°-220° C. at 6° C. per minute).

FIG. 2 is the NMR spectrum for fraction 5 of the foregoing distillationcontaining the compound having the structure: ##STR49## (Solvent: CFCl₃; Field strength: 100 MHz).

FIG. 3 is the infra-red spectrum for fraction 5 of the foregoingdistillation containing the compound having the structure: ##STR50##

EXAMPLE II Preparation of methacrylic acid ester of5-ethyl-tricyclo[2.2.1.0(2,6)heptan-2-ol ##STR51##

Into a 1 liter reaction flask equipped with stirrer, thermometer, refluxcondenser and heating mantle is placed a mixture of 30 mlborontrifluoride diethyletherate and 285 grams of methacrylic acid.While maintaining the reaction mass at 20° C. over a period of 30minutes, 340 grams of ethylidene norbornene is added with stirring. Thereaction mass is then maintained at 15°-20° C. with stirring for aperiod of 1 hour. At the end of the 1 hour period, the reaction mass isquenched with 500 ml water. The organic layer is separated from theaqueous layer and the organic layer is washed as follows:

i. 10% aqueous sodium chloride

ii. 10% aqueous sodium hydroxide

iii. 3 volumes of 10% sodium chloride

The reaction mass is then dried over anhydrous magnesium sulfate anddistilled on a 12"×1.5" Goodloe column to yield the following fractions:

    ______________________________________                                                  Vapor   Liquid                                                      Fraction  Temp.   Temp.      Pressure                                                                             Reflux                                    Number    (°C.)                                                                          (°C.)                                                                             mm/Hg. Ratio                                     ______________________________________                                        1         25/85   89/100     2.0    5:1                                       2         86      101        2.4    1:1                                       3         84      102        2.4    1:1                                       4         87      103        2.4    1:1                                       5         87      107        2.4    1:1                                       6         88      107        2.4    1:1                                       7         86      105        2.4    1:1                                       8         86      108        2.4    1:1                                       9         86      110        2.4    1:1                                       10        86      120        2.4    1:1                                       11        86      130        2.4    1:1                                       12        92      145        2.4    1:1                                       13        92      180        2.4    1:1                                       ______________________________________                                    

FIG. 4 is the GLC profile for the crude reaction product prior todistillation containing the compound having the structure: ##STR52##(conditions: SE-30 column programmed at 180° C. isothermal).

FIG. 5 is the NMR spectrum for fraction 3 of the foregoing distillationcontaining the compound having the structure: ##STR53## (Solvent: CFCl₃; Fieid strength: 100 MHz).

FIG. 6 is the infra-red spectrum for fraction 3 of the foregoingdistillation containing the compound having the structure: ##STR54##

EXAMPLE III Preparation of crotonic acid ester of5-ethyl-tricyclo[2.2.1.0(2,6)]heptan-1-ol ##STR55##

Into a 3 liter reaction flask equipped with thermometer, stirrer, refluxcondenser and heating mantle is placed a mixture of 300 grams ofanhydrous toluene and 30 ml borontrifluoride etherate. While maintainingthe reaction mass at 25° C., 344 grams of corotonic acid is slowlyadded. While maintaining the reaction mass at 25° C. and over a periodof 1 hour, 480 grams of ethylidene norbornene is added to the reactionmass with stirring.

The reaction mass is then stirred for a period of 0.5 hours. At the endof the 0.5 hour period, 500 ml water is added to the reaction mass.

The organic layer is separated from the aqueous layer and the organiclayer is washed as follows:

i. 500 ml 10% sodium carbonate

ii. water

The reaction mass is then distilled on a 12"×1.5" Goodloe column toyield the following fractions:

    ______________________________________                                                 Vapor   Liquid                                                       Fraction Temp.   Temp.     Pressure                                                                              Reflux                                     Number   (°C.)                                                                          (°C.)                                                                            mm/Hg   Ratio                                      ______________________________________                                        1        28/45    82/122   3       2:1                                        2        102     130       3       2:1                                        3        95      125       3       2:1                                        4        94      128       3       2:1                                        5        92      116       3       2:1                                        6        94      130       3       100% take off                              7        95      132       3       100% take off                              8        96      140       3       100% take off                              9        96      148       3       100% take off                              10       96      148       3       100% take off                              11       96      161       3       100% take off                              12       98      201       3       100% take off                              ______________________________________                                    

FIG. 7 is the GLC profile for the crude reaction product prior todistillation, containing the compounds having the structures: ##STR56##

FIG. 8 is the NMR spectrum for fraction 10 of the foregoing distillationcontaining the compounds having the structures: ##STR57## (Solvent:CFCl₃ ; Field strength: 100 MHz).

FIG. 9 is the infra-red spectrum for fraction 10 of the foregoingdistillation containing the compounds having the structures: ##STR58##

EXAMPLE IV Preparation of 3-methyl crotonic acid ester of5-ethyl-tricyclo[2.2.1.0(2,6)]heptan-1-ol ##STR59##

Into a 3 liter reaction flask equipped with stirrer, thermometer, refluxcondenser and heating mantle is placed a mixture of 400 grams ofsenecioic acid (4 moles), 300 grams anhydrous toluene and 30 mlborontrifluoride diethyletherate. Over a 1 hour period, whilemaintaining the reaction mass at 25°-30° C., 480 grams (4 moles) ofethylidene norbornene is added to the reaction mass. The reaction massis then stirred for 0.5 hours.

The reaction mass is then quenched with 1 liter of saturated sodiumchloride solution. The aqueous phase is separated from the organic phaseand the organic phase is then washed as follows:

i. One liter of 10% aqueous sodium carbonate

ii. One liter of sodium chloride

iii. 300 ml water

iv. One liter 10% sodium chloride.

The reaction mass is then dried over anhydrous magnesium sulfate anddistilled on a 12"×1.5" Goodloe column yielding the following fractions:

    ______________________________________                                                 Vapor   Liquid                                                       Fraction Temp.   Temp.     Pressure                                                                              Reflux                                     Number   (°C.)                                                                          (°C.)                                                                            mm/Hg   Ratio                                      ______________________________________                                        1        76/30    80/100   15/3    100% take off                              2        110     126       3       2:1                                        3        104     122       3       2:1                                        4        104     125       3       100% take off                              5        110     127       3       100% take off                              6        112     129       3       100% take off                              7        112     129       3       100% take off                              8        118     132       3       1005 take off                              9        118     135       3       100% take off                              10       120     138       3       100% take off                              11       122     138       3       100% take off                              12       125     145       3       100% take off                              13       125     148       3       100% take off                              14       125     158       3       100% take off                              ______________________________________                                    

FIG. 10 is the GLC profile for the crude reaction product of Example IVprior to distillation containing the compound having the structure:##STR60## (conditions: SE-30 column programmed at 150°-220° C. at 8° C.per minute).

FIG. 11 is the NMR spectrum for fraction 9 of the foregoing distillationcontaining the compound having the structure: ##STR61## (Solvent: CFCl₃; Field strength: 100 MHz).

FIG. 12 is the infra-red spectrum for fraction 9 of the foregoingdistillation containing the compound having the structure: ##STR62##

EXAMPLE V Pine needle perfume formulation

The following formulation is prepared:

    ______________________________________                                        Ingredients             Parts by Weight                                       ______________________________________                                        Turpentine gum oil      100                                                   Limonene                70                                                    Gum camphor             10                                                    Isobornyl acetate       50                                                    Borneol                 30                                                    2-(2-butenoyl)-3,3-dimethylnorbornane                                                                 40                                                    (produced according to Example XII                                            of U.S. Pat. No. 4,148,826)                                                    ##STR63##               100                                                   ##STR64##               70                                                    ##STR65##               30                                                   ______________________________________                                    

The compound produced according to Example II having the structure:##STR66## adds to this pine needle oil an excellent, powerful,long-lasting, green, herbaceous aroma which makes it more natural-like.

EXAMPLE VI Bergamot perfume

The following formulation is prepared:

    ______________________________________                                        Ingredients              Parts by Weight                                      ______________________________________                                        Bergamot oil stripped of 30                                                   bergaptans                                                                    Limonene                 70                                                   Citronellal coeur        20                                                   Citral                   14                                                    ##STR67##                82                                                  ______________________________________                                    

The compound produced according to Example IV having the structure:##STR68## adds to this bergamot formulation a powerful anisic naturalbergamot note reminiscent of freshly-harvested bergamot fruit.

EXAMPLE VII Patchouli perfume formulation

The following mixture is prepared:

    ______________________________________                                        Ingredients             Parts by Weight                                       ______________________________________                                        Orange oil              50                                                    Bergamot oil            20                                                    Lime oil                100                                                   Neroli oil               5                                                     ##STR69##                5                                                    ##STR70##               100                                                   ##STR71##               50                                                   Gamma methyl ionone     20                                                     ##STR72##               50                                                    ##STR73##               100                                                   ##STR74##               150                                                  ______________________________________                                    

The compounds of Examples I and III having the structures: ##STR75## addto this patchouli formulation an interesting, sophisticated, sweet,amber-like, violet flower-like and fruity aroma profile with green andherbaceous topnotes.

EXAMPLE VIII Rose formulation

To demonstrate the use of the compounds having the structures: ##STR76##produced according to Example III in a rose formulation, the followingformula is prepared:

    ______________________________________                                        Ingredients             Parts by Weight                                       ______________________________________                                        Phenylethyl alcohol     200                                                   Geraniol                400                                                   Trichloromethylphenyl carbinyl acetate                                                                20                                                    Phenylethyl acetate     60                                                    Undecylenic aldehyde (10% in diethyl                                                                   5                                                    phthalate)                                                                    n-nonyl aldehyde (10% in diethyl                                                                       2                                                    phthalate)                                                                    Musk ketone             10                                                    Musk ambrette           10                                                    Eugenol phenyl acetate  20                                                    Citronellol             100                                                   Vanillin (10% in diethyl phthalate)                                                                   30                                                    Eugenol                 30                                                    Citronellyl formate     30                                                    Geranyl acetate         10                                                    Linalool                40                                                    Geranyl phenyl acetate  50                                                    Cis beta,gamma-hexenyl acetate                                                                         2                                                     ##STR77##                5                                                   ______________________________________                                    

The addition of 0.5% of the mixture of compounds having the structures:##STR78## prepared according to Example III lends a great deal ofstrength and character to the rose fragrance. It contributes the greatfloralcy and heady natural sweetness of the red rose flower togetherwith green and fruity nuances and sweet, floral topnotes.

At lower concentrations (0.01%), this mixture of compounds' contributionis more subtle, however, it still gives an interesting natural effectwith the violet flower-like undertone.

The product may normally be used from approximately 0.01% to 10% inperfume compositions. For special effects, however, higherconcentrations (50% plus) can be used.

EXAMPLE IX Preparation of soap compositions

One hundred grams of soap chips are produced according to Example V ofU.S. Pat. No. 4,058,487 issued on Nov. 15, 1977, the specification forwhich is incorporated herein by reference, as follows:

The sodium salt of an equal mixture of C₁₀ -C₁₄ alkane sulfonate (95%active), 40 pounds, is dissolved in a mixture of 80 pounds of anhydrousisopropanol and 125 pounds of deionized water at 150° F. In this mixtureis dissolved 10 pounds of partially hydrogenated coconut oil fatty acidsand 15 pounds of sodium mono-C₁₄ alkyl maleate, and the pH of thissolution is adjusted to 6.0 by the addition of a small amount of 50%aqueous solution of sodium hydroxide. The isopropanol is distilled offand the remaining aqueous solution is drum dried. The resulting solidactives are then blended in a chip mixture with 10 pounds of water, 0.2pounds of titanium hydroxide and 0.7 pounds of one of the perfumeingredients set forth in Table II below. The chips are then plodded intologs, cut to size and finally stamped into bars having a pH ofapproximately 6.9.

Each of the perfumed soaps produced by means of the foregoing proceduremanifests an excellent aroma as set forth in Table II infra.

                  TABLE II                                                        ______________________________________                                        Ingredient             Fragrance Profile                                      ______________________________________                                        Perfume composition of A pine needle aroma                                    Example V              with powerful long-                                                           lasting green,                                                                herbaceous nuances.                                    Perfume composition of A natural, fresh,                                      Example VI             bergamot oil aroma                                                            with powerful anisic                                                          nuances.                                               Perfume composition of A patchouli aroma                                      Example VII            with sweet, anisic,                                                           amber-like, violet                                                            flower-like, green                                                            and fruity                                                                    undertones.                                            Perfume composition of A rose aroma with a                                    Example VIII           floral, green, fruity                                                         topnote profile and                                                           a violet-like                                                                 undertone.                                              ##STR79##             A sweet, anisic, amber-like aroma with green,                                 herbaceous topnotes.                                    ##STR80##             A powerful, long- lasting, green, herbaceous                                  aroma.                                                  ##STR81##             A floral (violet-like), green, fruity aroma.            ##STR82##             A powerful, anisic, bergamot-like, fruity aroma                               with citronnelal like undertones.                      ______________________________________                                    

EXAMPLE X Preparation of a detergent composition

A total of 100 grams of a detergent powder prepared according to U.S.Pat. No. 4,058,472 (the specification for which is incorporated byreference herein) and containing 5% by weight of the sodium salts of amixture of sulfonated C₁₄ -C₁₈ alkyl catechol as a surface activecomponent, the mixture being 60 parts by weight of mono-C₁₄ -C₁₈ alkylcatechol and 40 parts by weight of di-C₁₄ -C₁₈ alkyl catechol, 35%sodium tetrapyrophosphate, 30% sodium silicate, 20% of sodium carbonate,3% of sodium carboxymethyl cellulose and 7% of starch is mixed with 0.15grams individually with each of the aroma ingredients set forth in TableII of Example IX until a substantially homogeneous composition isobtained. Each of the compositions has an excellent aroma as set forthin Table II of Example IX.

EXAMPLE XI Preparation of a cosmetic powder composition

A cosmetic powder is prepared by mixing in a ball mill, 100 grams oftalcum powder with 0.25 grams of each of the perfume materials of TableII of Example IX. Each of the powders has an excellent aroma as setforth in Table II of Example IX.

EXAMPLE XII Perfumed liquid detergent

Concentrated liquid detergents with aromas as set forth in Table II ofExample IX are prepared by adding 0.10%, 0.15% and 0.20% of each of theingredients set forth in Table II of Example IX. They are prepared byadding and homogeneously mixing the appropriate quantity of perfumesubstance of Table II of Example IX in the liquid detergent. Thedetergents individually possess aromas as set forth in Table II ofExample IX, the intensity increasing with greater concentrations ofperfume substance set forth in Table II of Example IX.

EXAMPLE XIII Preparation of a cologne and handkerchief perfume

Each of the ingredients of Table II of Example IX is incorporatedindividually into colognes of several strengths at concentrations of2.0%, 2.5%, 3.0%, 3.5%, 4.0% and 5.0% in 75%, 80%, 85%, 90% and 95%aqueous ethanol; and into several concentrations of handkerchiefperfumes at the rates of 15%, 20% and 25% (in 80%, 85%, 90% and 95%aqueous ethanol). Distinct and definite aromas as set forth in Table IIof Example IX are imparted to the colognes and to the handkerchiefperfumes at the several concentrations set forth above.

EXAMPLE XIV Preparation of soap compositions

One hundred grams of soap chips (IVORY® produced by the Proctor & GambleCompany of Cincinnati, Ohio) are admixed with one gram of each of thesubstances set forth in Table II of Example IX supra until homogeneouscompositions are obtained. In each of the cases, the homogeneouscompositions are heated under 3 atmospheres pressure at 180° C. for aperiod of three hours and the resulting liquids are placed into soapmolds. The resulting soap cakes, on cooling, manifest excellent aromasas set forth in Table II of Example IX.

EXAMPLE XV Preparation of solid detergent compositions

Detergents are prepared from the following ingredients according toExample I of Canadian Pat. No. 1,007,948, the specification for which isincorporated by reference herein:

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                         ##STR83##            12                                                      Sodium carbonate     55                                                       Sodium citrate       20                                                       Sodium sulfate, water brighteners                                                                  q.s.                                                     ______________________________________                                    

This detergent is a "phosphate-free" detergent. A total of 100 grams ofsaid detergent is admixed with 0.10, 0.15, 0.20 and 0.25 grams of eachof the substances set forth in Table II of Example IX supra. Each of thedetergent samples has an excellent aroma as indicated in Table II ofExample IX.

EXAMPLE XVI Preparation of drier-added fabric softener article

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396 the specification for which is incorporated by referenceherein, a non-woven cloth substrate useful as a drier-added fabricsoftening article of manufacture is prepared wherein the substrate,substrate coating and outer coating and the perfume material are asfollows:

1. a water "dissolvable" paper ("Dissolvo Paper") as the substrate;

2. Adogen 448® (melting point about 140° F.) as the first substratecoating; and

3. an outer coating having the following formulation (melting pointabout 150° F.):

57% C₂₀ -C₂₂ HAPS;

22% isopropyl alcohol;

20% antistatic agent;

1% of one of the perfumery substances set forth in Table II of ExampleIX supra.

Fabric softening compositions containing the substances as set forth inTable II of Example IX supra essentially consist of a substrate having aweight of about 3 grams per 100 square inches; a substrate coatingweighing about 1.85 grams per 100 square inches of substrate; and anouter coating weighing about 1.5 grams per 100 square inches ofsubstrate are prepared thereby providing a total aromatized substrateand outer coating weight ratio of about 1:1 by weight of the substrate.

The aromas as set forth in Table II of Example IX supra are imparted ina pleasant manner to the head space in a drier on operation thereofusing the said drier-added fabric softening non-woven fabric by addingto the drying cycle.

As stated above in the case of fabric softener articles, the entire U.S.Pat. No. 3,632,396 is incorporated by reference herein. Thus, all of thearticles of U.S. Pat. No. 3,632,396 acting as fabric softening articlesin said U.S. Patent may be perfumed in their outer coating with from0.25% up to 5% by weight of each of the perfumimg substances of Table IIof Example IX supra.

EXAMPLE XVII Hair preparation

A "soft-feel, good-hold" hair spray is produced containing the followingingredients:

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                         ##STR84##            4.00                                                    Anhydrous ethanol    70.90                                                    Dioctyl sebecate     0.05                                                     Benzyl alcohol       0.05                                                      ##STR85##            24.95                                                    ##STR86##            0.05                                                    ______________________________________                                    

The PVP/VA copolymers are first dissolved in alcohol and all otheringredients are added until uniform. The propellant is then pressurizedand used as an aerosol. The resulting hair sprays each have pleasantaromas as set forth in Table II of Example IX.

EXAMPLE XVIII Scouring cleanser composition

A scouring cleanser composition is prepared in accordance with Example Iat columns 11 and 12 of U.S. Pat. No. 4,193,888 issued on Mar. 18, 1980,the specification for which is incorporated by reference herein. To thiscomposition, the substances set forth in Table II of Example IX supraare added at the level of 0.25% as set forth in the table in saidExample I of U.S. Pat. No. 4,193,888 yielding an aroma on using saidcleanser in ordinary circumstances which is quite pleasant and describedin Table II of Example IX supra.

EXAMPLE XIX

A fabric softening article prepared substantially as set forth inExample XIII of Canadian Pat. No. 1,069,260, the specification for whichis incorporated by reference herein, is prepared containing 0.21% byweight of a perfuming substance as set forth in Table II of Example IXsupra and yielding on use in a drier, a faint aroma as set forth inTable II of Example IX supra.

EXAMPLE XX Tobacco flavor formulations

Cigarettes are produced using the following tobacco formulations:

    ______________________________________                                        Ingredients    Parts by Weight                                                ______________________________________                                        Bright         40.1                                                           Burley         24.9                                                           Maryland       1.1                                                            Turkish        11.6                                                           Stem (flue cured)                                                                            14.2                                                           Glycerine      2.8                                                            H.sub.2 O      5.3                                                            ______________________________________                                    

At the rate of 0.2%, the following tobacco formulation is applied to allof the cigarettes produced with the above tobacco formulation:

    ______________________________________                                        Ingredients     Parts by Weight                                               ______________________________________                                        Ethyl butyrate  0.05                                                          Ethyl valerate  0.05                                                          Maltol          2.00                                                          Cocoa extract   26.00                                                         Coffee extract  10.00                                                         Ethyl alcohol (95%)                                                                           20.00                                                         H.sub.2 O       41.90                                                         ______________________________________                                    

To portions of 50% of the cigarettes at levels of 10 and 20 ppm, thecompound of Example IV having the structure: ##STR87## is added. Thesecigarettes are hereinafter called "experimental" cigarettes. Thecigarettes without the compound of Example IV having the structure:##STR88## are hereinafter called "control" cigarettes. The controlexperimental cigarettes are then evaluated by paired comparison and theresults are as follows:

a. In aroma, the experimental cigarettes are all found to be morearomatic with Turkish tobacco-like nuances.

b. In smoke flavor, the experimental cigarettes are all found to be morearomatic, more sweet with Turkish tobacco, oriental-like nuances thanthe control cigarettes.

The experimental cigarettes containing 20 ppm of the compound having thestructure: ##STR89## are found to be fruity and have pleasantaesthetically pleasing licorice-like notes in addition.

EXAMPLE XXI Basic oral hygiene flavor formulation

The following basic oral hygiene flavor formulation is prepared:

    ______________________________________                                        Ingredients     Parts by Weight                                               ______________________________________                                        Peppermint oil  89.0                                                          Spearmint oil   2.0                                                           Clove oil       1.0                                                           Anethol         2.0                                                           Cardamom oil    0.1                                                           Wintergreen oil 5.0                                                           Cinnamic aldehyde                                                                             0.9                                                           ______________________________________                                    

The basic oral hygiene flavor formulation is now divided into two parts.To the first part at the rate of 10% is added the compound having thestructure: ##STR90## produced according to Example I. To the secondpart, nothing is added. The flavor with the addition of the materialproduced according to Example I having the structure: ##STR91## has afresher, sweet, licorice, anise oil-like, spicy aroma and tastecharacteristic. The peppermint characteristics also appear to beenhanced. Therefore, the flavor with the material produced according toExample I having the structure: ##STR92## is preferred by a bench panel.

EXAMPLE XXII Green salad dressing flavor

The following flavor formulation is prepared:

    ______________________________________                                                                 Parts by                                             Ingredients              Weight                                               ______________________________________                                        Black pepper oil         4                                                    Nutmeg oil               3                                                    Celery oil               3                                                    Lemon oil                3                                                    Mustard oil              1                                                    Vinegar-citric acid (50:50 mixture)                                                                    120                                                  Starch paste prepared from                                                                             300                                                  tapioca flour-water (50:50 mixture)                                           Liquid egg yolks         210                                                  Sodium chloride          7                                                    Sucrose                  10                                                   Mustard                  20                                                   Locust bean gum          6                                                     ##STR93##                2                                                    ##STR94##                                                                     ##STR95##                3                                                   ______________________________________                                    

The addition of the compounds produced according to Exemple II or III tothis green salad dressing formulation causes the salad dressing to havea fresh, dandelion leaf, raw spinach nuance. The use of the compound ofExample II having the structure: ##STR96## in addition, imparts faint,scallion-like nuances to the salad dressing.

When the resulting salad dressing flavor is incorporated into a saladdressing in the standard way and the salad dressing is used on a greensalad, interesting dandelion leaf, raw spinach nuances are imparted tothe overall salad even in the absence of dandelion leaf and spinach.

EXAMPLE XXIII Licorice chewing stick

A flexible licorice stick is prepared in a standard manner. Prior tohardening, at the level of 0.05 ppm, the compound of Example IV havingthe structure: ##STR97## is added to the molten mixture. The moltenmixture is molded into licorice sticks and hardened for marketing. Eachof the licorice sticks has a pleasant, powerful, natural-like licoriceanisic, China Star Anise Oil-like flavor. No China Star Anise Oil wasused in producing these licorice sticks.

What is claimed is:
 1. At least one compound defined according to thestructure: ##STR98## wherein one of the dashed lines represents acarbon-carbon bond and the other of the dashed lines represents no bond;wherein the wavy lines represent a "cis" or a "trans" juxtaposition ofthe R₁, R₂, R₃ and carboalkoxy moieties around the carbon-carbon doublebond; wherein R₁, R₂ and R₃ each represent methyl or hydrogen with theproviso that at least one of R₁, R₂ and R₃ is hydrogen.
 2. The compoundof claim 1 defined according to the structure: ##STR99## wherein R₁, R₂and R₃ is methyl or hydrogen and at least one of R₁, R₂ and R₃ ishydrogen.
 3. The compound of claim 1 having the structure: ##STR100## 4.The compound of claim 1 having the structure: ##STR101##
 5. The compoundof claim 1 having the structure: ##STR102##
 6. The compound of claim 1having the structure: ##STR103##
 7. The compound of claim 1 having thestructure: ##STR104##
 8. A product produced according to the process ofintimately admixing ethylidene norbornene having the structure:##STR105## with an acrylic acid derivative having the structure:##STR106## in the presence of a Lewis acid or protonic acid catalyst.The temperature of reaction varying from about 25° C. up to about 120°C.; the mole ratio of acid catalyst to ethylidene norbornene varyingfrom about 1:99 up to about 1:10; and the mole ratio of ethylidenenorbornene reactant:acrylic acid derivative reactant varying from about1:1 up to about 1:2.
 9. The product produced according to claim 8wherein in the process for producing said product the process is carriedout in the presence of a Lewis acid catalyst and the Lewis acid catalystis borontrifluoride diethyletherate.
 10. A process for augmenting orenhancing the aroma of a consumable material selected from the groupconsisting of perfume compositions and colognes comprising the step ofadding to a perfume composition or cologne an aroma augmenting orenhancing quantity of at least one compound defined according to claim1.